ES2222460T3 - POLYMER OR POLYESTER OLIGOMER WITH CARBAMATE FUNCTIONALITY THAT HAS SIDE CARBAMATE GROUPS. - Google Patents

Abstract

POLYESTER POLYMERS DESCRIBING PENDING CARBAMATE GROUPS ARE DESCRIBED. THE POLYMERS ARE PREPARED THROUGH THE REACTION OF A POLYOL THAT HAS AT LEAST A PENDING CARBAMATE GROUP WITH A POLYMYCDE TO FORM A POLYESTER THAT HAS PENDING CARBAMATE GROUPS.

Description

Polymer or polyester oligomer with carbamate functionality that has lateral carbamate groups.

Field of the Invention

This invention relates to polymers, and in in particular to hardenable coating compositions that they contain said polymers.

Background of the invention

Polymers and oligomers containing groups with carbamate functionality have been used in a wide variety of hardenable compositions. For example, in the United States Patent United 5,356,669 and in WO 94/10211 acrylic polymers are described with carbamate functionality. These can be prepared by addition polymerization of acrylic monomers with functionality carbamate or by transcarbamylation of an acrylic with funcinoality hydroxyl with an alkyl carbamate. Polyesters with carbamate functionality prepared by transcarbamylation of a hydroxy-functional polyester are described in JP 4/4124.

Polyesters are widely used in hardenable compositions such as compositions of coating. These resins offer many properties helpful, such as long durability, good flexibility, good dispersibility in aqueous systems by incorporating appropriate ionic or non-ionic stabilizing groups, resistance to impacts, good adhesion and other physical properties such as relaxation of tensions. A field of interest regarding polyester resins for hardenable compositions has been the incorporation, within the resin, of sufficient levels of functional groups that allow the desired performance of hardening. Hydroxyl groups are commonly used as functional groups in hardenable compositions, but resins Polyester with side hydroxyl groups are difficult to prepare since any lateral hydroxyl group would be consumed by reaction with the acid groups during the formation of the polyester. The hydroxyl functional groups are incorporated usually in polyester resins by agents that hinder the polyol, such as trimethylolpropane, which generates OH terminal groups, but not OH side groups. These resins provide only a crosslink density limited to hardening. The crosslinking density can be increased by little by using branched polyesters, which prepare by incorporating polyols or trifunctional polyacids or superior in the polyester reaction mixture. However the degree of branching is often limited due to the gelation Often, the low density of crosslinking in hardenable polyester resin systems must be compensated through the use of higher molecular weight resins, which look much more like thermoplastic compositions than thermosetting compositions.

Polyesters with carbamate functionality are described in JP 51/4124. This document describes the preparation of polyesters with terminal carbamate groups by transesterification of a polyester Classic hydroxy-functional with a carbamate of I rent.

Accordingly, the present invention focuses on a new method of preparing polymers or polyester oligomers which carry lateral carbamate groups.

Summary of the Invention

In accordance with the present invention, provides a method for the preparation of polymers or oligomers of polyester comprising the reaction of a polyol having multiple lateral carbamate groups with a polyacid to form a polyester with side carbamate groups.

In another embodiment of the invention, provide polyester polymers or oligomers prepared according to The method mentioned above.

Even more, in another embodiment of the invention, provide hardenable coating compositions that comprise the polyester with carbamate functionality above described and a hardening agent reactive with the group carbamate

Description of the preferred embodiments

The polyol with multiple carbamate groups can Prepare in many ways. One method is to submit reaction a compound that has various cyclic carbonate groups with ammonia, ammonium hydroxide, or with a primary amine to break the ring of cyclic carbonate groups. This reaction of ring rupture converts each ring cyclic carbonate into a hydroxylated group and a pending carbamate group.

The compound that has multiple carbonate groups Cyclics can be prepared in different ways. A technique consists in reacting a polyisocyanate or a polyanhydride with a cyclic hydroxyalkyl carbonate. Carbonates of cyclic hydroxyalkyl can be prepared by several procedures Some cyclic hydroxyalkyl carbonates, such as 3-hydroxypropyl carbonate (i.e. glycerin carbonate), are commercially available. The cyclic carbonate compounds can be synthesized by Any of the different procedures. A procedure implies the reaction of a compound containing an epoxide group with CO2, preferably under pressure, with a catalyst. The Useful catalysts include those that activate a ring oxirane, such as tertiary quaternary amine salts (for example, tetramethyl ammonium bromide), salts tin and / or phosphorus complexes (for example, (CH 3) 3 SnI, (CH 3) 4 PI). Epoxides they can also undergo reaction with β-butyrolactone in the presence of these catalysts In another procedure, a glycol, such as glycerin, is reacts at temperatures of at least 80 ° C (usually at reflux) with diethyl carbonate in the presence of a catalyst (for example, potassium carbonate) to form a carbonate of hydroxyalkyl Alternatively, a functional compound that It contains a 1,2-diol ketal with the structure:

one

can undergo ring break with water at temperatures of at least 60 ° C, preferably in presence of traces of acid, to form a 1,2-glycol, which then reacts with carbonate diethyl to form carbonate cyclic.

Cyclic carbonates normally have rings of 5-6 elements, as known in the technique. 5 element rings are preferred, due to their ease of synthesis and greater degree of commercial availability. The  Preferred cyclic hydroxyalkyl carbonates, used in the practice, they can be represented by the formula:

2

where R is a hydroxyalkyl group from 1 to 18 carbon atoms, preferably from 1 to 6 atoms of carbon and especially 1 to 3 carbon atoms and n is 1 or 2, the which may be substituted with one or more different substituents as blocked amines or unsaturated groups. In particular, R is -C m H 2m OH, the hydroxyl being able to be primary or secondary and m is 1 to 8, and even more preferably, R is - (CH 2) p -OH, where the hydroxyl is primary and p is 1 a 2.

The organic polyisocyanate that can be reacted with the cyclic hydroxyalkyl carbonate is essentially any polyisocyanate, and preferably a diisocyanate, for example hydrocarbon diisocyanates or substituted hydrocarbon diisocyanates. Many of these organic diisocyanates are known in the art, including p- phenylene diisocyanate, biphenyl 4,4'-diisocyanate, toluene diisocyanate, 3,3'-dimethyl-4,4-biphenylene diisocyanate, 1-diisocyanate , 4-tetramethylene, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, methylene bis (phenyl isocyanate), naphthalene 1,5-diisocyanate, bis (isocyanate ethyl fumarate), diisocyanate Isophorone (IPDI), tetramethylxylene diisocyanate, and methylene-bis (4-cyclohexyl isocyanate). Diol terminated isocyanate adducts, such as ethylene glycol, 1,4-butylene glycol, etc., may also be used. These are formed by reacting more than one mole of a diisocyanate, such as those mentioned, with one mole of a diol to form a longer chain diisocyanate. Alternatively, the diol may be added together with the diisocyanate.

Although diisocyanates are preferred, they may use other multifunctional isocyanates. As examples are cite benzene and polymethylene 1,2,4-triisocyanate polyphenyl isocyanate.

The polyisocyanate and carbonate reaction of cyclic hydroxyalkyl can be carried out under conditions known in the art for the reaction of alcohols and isocyanates

Polyanhydrides that can undergo reaction with a cyclic hydroxyalkyl carbonate include any of various compounds well known in the art, for example hexahydrophthalic anhydride, anhydride methylhexahydrophthalic, maleic anhydride, glutamic anhydride, 1,2,4,5-bis-anhydride of cyclohexane The conditions for this reaction are generally of at least 80 ° C, preferably 98-120 ° C, in presence of a metallic tin catalyst.

Compounds that carry multiple groups cyclic carbonate can also be easily prepared by reaction of a polyepoxide with carbon dioxide to convert epoxy groups in cyclic carbonate groups. Polyepoxides are well known in the art. Among the useful polyepoxides are include epoxidized trimethylolpropane by reaction with a epihalohydrin, and also epoxy-novolacs. They can also use oligomeric or polymeric polyepoxides, such as acrylic polymers or oligomers containing methacrylate of glycidyl or epoxy terminated polyglycidyl ethers. They can also use other polyepoxides, for example epoxy-novolacs. As with other polyepoxides, the epoxy-novolacs can be reacted with carbon dioxide to form the cyclic carbonate compound.

Although linear polyesters are based mainly in compounds that have two functional groups for the esterification reaction, carbonates are also contemplated cyclic with functionality greater than 3 to provide branched polyesters. For example, isocyanate groups in a diisocyanate, such as isophorone diisocyanate, can be added to a polyol, such as trimethylolpropane, to produce a tetrafunctional alcohol that can be epoxidized with a epihalohydrin to produce a tetrafunctional polyepoxide, which at in turn is reacted with carbon dioxide to form a tetrafunctional cyclic carbonate. Other polyepoxides of superior functionality, for example the tetrakis (4-glycidyloxyphenyl) ethane, they can also be reacted with CO2 to form polycyclic carbonates.

The compound with multiple carbonate groups Cyclic is reacted with ammonia, ammonium hydroxide or With a primary amine. This reaction is carried out under conditions mild (for example, at 0-60 ° C in water, methanol or other known solvents). The reaction with ammonia or hydroxide Ammonium produces a primary carbamate and is preferred.

The reaction with a primary amine produces a N-substituted secondary carbamate. The reaction of ring rupture due to ammonia, ammonium hydroxide or amine primary, the cyclic carbonate group produces such a carbamate group as described above and also a hydroxyl group primary or secondary, which participates in the formation reaction of the polyester in the next step of the invention. This product of reaction thus comprises lateral carbamate groups and hydroxyl terminal groups.

The side carbamate groups of polyester The present invention may be primary or secondary groups. Primary carbamate groups can be represented by the formula:

\uelm{C}{\uelm{\dpara}{O}}

---NH2---OR---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- NH2

and secondary carbamate groups can be represented by the formula:

\uelm{C}{\uelm{\dpara}{O}}

---NHR---OR---

 \ uelm {C} {\ uelm {\ dpara} {O}} 

--- NHR

where R is an alkyl group, substituted or unsubstituted, from 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and especially 1 carbon atom, or cycloaliphatic. It should be understood that terms alkyl and cycloalkyl should include alkyl and substituted cycloalkyl, such as alkyl or cycloalkyl substituted by halogen or unsaturated alkyl substituted by a group. Substituents that have an adverse impact on Hardenable material properties, however, should be avoided. Primary carbamates form in the breakdown reactions of ring of cyclic carbonates, described above, by ammonia or ammonium hydroxide as a breakdown reagent of ring.

In accordance with the present invention, a mixture comprising the polyol with multiple side carbamate groups and a polyacid is reacted to form a polyester. The polyacids useful in the practice of the invention may contain about 2 to 34 carbon atoms aliphatic or aromatic groups, and at least 2, preferably not more than 4, carboxyl groups, which may optionally be present in the form of anhydride groups. The polyacids can be polyacids per se or cyclic anhydrides of polyacids, the ring of which can be broken by the diol containing carbamate or other polyols during the reaction of the polyester to form acid groups for the condensation of the polyester. Examples of useful polyacids include phthalic anhydride, terephthalic acid, isophthalic acid, adipic acid, succinic acid, glutaric acid, fumaric acid, maleic acid, cyclohexanedioic acid, trimellitic anhydride, azelaic acid, sebacic acid, dimeric acid, dianitic acid, pyridic acid substituted maleic and fumaric such as citraconic, chloromaleic or mesaconic acids and substituted succinic acids such as aconitic and iraconic acids. Mixtures of polyacids can be used.

The polyester reaction mixture can also comprise additional polyols. The amount of this polyol additional is determined by the desired level of functionality Carbamate for polyester. Useful polyols contain generally more than 2, preferably 2 to about 10 carbon atoms, especially about 2 to 8 atoms of carbon, in addition to having 2 to about 6, preferably from 2 to about 4 hydroxyl groups. Some examples of preferred polyols are one or more of the following: neopentyl glycol, ethylene glycol, propylene glycol, butanediol, hexamethylene diol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, trimethylolpropane, pentaerythritol, diethylene glycol neopentyl glycolhydroxypivalate, triethylene glycol, tetraethylene glycol, dipropylene glycol, polypropylene glycol, hexylene glycol, 2-methyl-2-ethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol,  1,5-pentanediol, thiodiglycol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 2,2,4-trimethyl-1,3-pentanediol,  1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glycerol, trimethylolpropane, trimethylolethane, 1,2,4-butanotriol, 1,2,6-hexanotriol, dipentaerythrite, tripentaerythrite, mannitol, sorbitol, methylglucoside, compounds similar evident to those skilled in the art, and mixtures thereof. According to the desired properties for the final resin, some other polyols can be incorporated into the mixture of reaction, such as fatty polyols, phenolic polyols (by example, hydroquinone, phenolphthalein, bisphenol A), polyols oligomeric or polymeric (for example, polyester polyols preformed) In addition, other components, such as modifiers of reaction, catalysts, solvents, dispersing agents and similar as is known in the art.

The proportions of polyacid, polyol with lateral carbamate and any other active compound may be chosen so that an acid terminated polyester is provided or a hydroxyl terminated. This can be done by use of a stoichiometric excess of polyacid or polyol.

If water solubility is desired, it is important to build stabilizing groups in water within the polyester. This can be done by incorporating water stabilizing polyether polyols within the mixture of reaction, so that they are incorporated into the polyester, or by  the use of dimethylpropionic acid as a polyol in the reaction mixture.

An intermediate resin of polyester having hydroxyl or acid end groups by the use of an excess of polyacid component or polyol in the polyester reaction mixture. The terminal groups of the resin can then be controlled by reaction of those groups terminals with an excess of an impeding agent, such as Knows in the art. If the intermediate resin has an acid terminal, a monofunctional or multifunctional alcohol can be used to terminate the reaction (prevent free acid groups) by desired level (determined by the viscosity and concentration of the isocyanate groups present). They can also be used also multifunctional alcohols, such as ethylene glycol, trimethylolpropane and hydroxyl terminated polyesters. Whether it is a resin with only carbamate functionality and without hydroxyl functionality, the polyester intermediate resin is Prevents, preferably, with a monofunctional alcohol (for example, n-butanol). Similarly, an intermediate resin terminal hidoxyl can be prevented by reaction with an excess of monofunctional or polyfunctional acid.

The polyesterification reactions are carried to normally run at temperatures between 140ºC and 260ºC, and for a time ranging from 3 to 15 hours, with or without the use of acid esterification catalysts such as phosphorous acid or toluenesulfonic acid present in proportions of 0.01 to 2.0 percent by weight. Optionally, the reaction is carried out in the presence of a solvent, such as a hydrocarbon aromatic, as is known in the art. Reaction can be performed in a single stage or in multiple stages, such as a Two stage reaction. The polyesters so produced have generally a number average molecular weight between 1000 and 60,000.

The polyester resin prepared according to the invention can be incorporated into a hardenable composition, such as a coating composition. In a composition hardenable according to the invention, the hardening is effect by reaction of the polyester component with carbamate functionality with a component (2) that is a compound with multiple functional groups reactive with carbamate groups lateral, on the polyester. These reactive groups include methylol or methyl alkoxy groups active on the agents cross-linking aminoplastics or other compounds, such as phenol / formaldehyde adducts, siloxane groups and anhydride groups. How  Examples of hardening agents include resin formaldehyde-melamine (including resin monomeric or polymeric melamine and partial or melamine resin completely rented), urea resins (for example, methylolureas such as formaldehyde-urea resin, alkoxyureas such as formaldehyde-urea resin butylated), polyanhydrides (for example, polysuccinic anhydride) and polysiloxanes (for example, trimethoxysiloxane). Are especially preferred aminoplast resins, such as resin formaldehyde-melamine or resin formaldehyde-urea.

In a hardenable composition employed in the practice of the present invention can optionally be used a solvent Although the composition used according to the The present invention can be used, for example, in the form of a powder substantially solid, or of a dispersion, is often desirable that the composition is in a substantially state liquid, which can be achieved by using a solvent This solvent should act as such with respect to to polyester with carbamate functionality as with respect to hardening agent. In general, according to the properties of solubility of the components, the solvent can be any organic solvent and / or water. In a preferred embodiment, the Solvent is a polar organic solvent. Especially the solvent is an aliphatic polar solvent or a polar solvent aromatic. In particular, the solvent is a ketone, an ester, a acetate, an aprotic amide, an aprotic sulfoxide or an amine aprotic Examples of useful solvents include ethyl methyl ketone, isobutyl methyl ketone, acetate m-amyl, ethylene glycol butyl ether acetate, propylene glycol monomethyl ether acetate, xylene, N-methylpyrrolidone or hydrocarbon mixtures aromatic In another preferred embodiment, the solvent is water or a mixture of water with small amounts of co-solvents

The curable composition used in the practice of the invention may include a catalyst to increase the hardening reaction. For example, when aminoplast compounds, especially monomeric melamines, are used, a strong acid catalyst can be used to increase the hardening reaction. These catalysts are well known in the art and include, for example, p- toluenesulfonic acid, dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid, phenyl acid phosphate, monobutyl maleate, butyl phosphate and hydroxy phosphate ester. Strong acid catalysts are often blocked, for example with an amine. Other catalysts that may be useful in the composition of the invention include Lewis acids, zinc salts and tin salts.

In a preferred embodiment of the invention, the Amount of solvent present in the curable composition is about 0.01 percent by weight to about 99 percent by weight, preferably from about 10 percent by weight up to about 60 percent by weight, and especially from about 30 percent by weight to  approximately 50 percent by weight.

The coating compositions can apply to the article by any of the techniques well known. These include, for example, coating by spray, immersion, roller, curtain coating, and the like For engine box panels the spray coating.

Any additional agent used, by example, surfactants, fillers, stabilizers, agents humidifiers, dispersing agents, adhesion promoters, UV absorbers, HALS, etc., can be incorporated into the coating composition. Although the agents are well known In the prior art, the amount used must be controlled for prevent it from adversely affecting the characteristics of coating.

The hardenable composition according to the invention is preferably used in a very coating bright and / or as a transparent coating on a coating Color-plus-transparency compound. Very bright coatings, as cited here, are coatings that have a brightness of 20º (ASTM D523-89) or a DOI (ASTM E430-91) of at least 80. The curable composition according to the invention It can also be used as the base coating of a compound coating color-plus-transparency.

When the coating composition of the invention is used as a pigmented paint coating very bright, the pigment can be any organic compound or inorganic or colored materials, fillers, laminated materials metallic or other inorganic as mica or aluminum scales, and other materials of the type that the technique normally calls pigments The amount of pigments commonly used in the composition varies from 1% to 100%, based on the total solid weight of components A and B (that is, a P: B ratio of 0.1 to 1).

When the coating composition agreed with the invention it is used as a transparent layer of a compound coating color-plus-transparency, the composition of the pigmented base layer can be any of well known in the art and does not require any detailed explanation Polymers known in the art for being useful in base coat compositions include acrylics, vinyls, polyurethanes, polycarbonates, polyesters, alkyds and polysiloxanes Preferred polymers include acrylics and polyurethanes In a preferred embodiment of the invention, the base layer composition also uses an acrylic polymer with carbamate functionality. The base layer polymers can be thermoplastics, but are preferably crosslinkers and comprise one or more types of crosslinking functional groups. These groups include, for example, hydroxyl, isocyanate, amine, epoxy groups, acrylate, vinyl, silane and acetoacetate. These groups can be masked or locked so that they are unlocked and are available for the crosslinking reaction under the conditions of desired hardening, generally at elevated temperatures. The Useful crosslinking functional groups include hydroxyl groups, epoxy, acid, anhydride, silane and acetoacetate. The groups Preferred functional crosslinkers are the groups of hydroxyl and amino functionality.

The base layer polymers can be self-crosslinking agents or may require a crosslinking agent separated reactive with the functional groups of the polymer. When the polymer comprises hydroxyl functional groups, for example, the crosslinking agent can be an aminoplast resin, isocyanate and blocked isocyanates (including isocyanurates), and acid or anhydride functional crosslinking agents.

Preferably, the compositions of coating described here are subject to conditions that allow to harden the coating layers. Although they can several hardening methods are used, the thermal hardening Generally, thermal hardening is effect by exposure of the coated article at temperatures high from mainly radiant heat sources. Hardening temperatures will vary according to groups. blocking particulars used in crosslinking agents, although they usually oscillate between 93ºC and 177ºC. The compounds according with the present invention they are reactive even at temperatures of relatively low hardening. Thus, in one embodiment preferably, the hardening temperature is preferably between 115 ° C and 150 ° C, and especially between 115 ° C and 138 ° C for a blocked acid catalyzed system. For a non-blocked acid catalyzed system, the hardening temperature preferably ranges between 82 ° C and 99 ° C. The hardening time will vary according to the components particulars used and physical parameters such as the thickness of layer, however, typical healing times range between 15 and 60 minutes, and preferably 15-25 minutes for systems catalyzed by blocked acid and from 10-20 minutes for systems catalyzed by unblocked acid.

Claims (15)

1. Method for preparing a polyester that has lateral carbamate groups that involves the reaction of a mixture that it comprises a polyol, which is obtained by reacting a composed of multiple cyclic carbonate groups with ammonia, ammonium hydroxide or with a primary amine to break the ring of the cyclic carbonate groups, to form a polyol that has multiple lateral carbamate groups, and a polyacid to form a polyester with side carbamate groups. 2. Method according to claim 1, characterized in that the compound having multiple cyclic carbonate groups is prepared by reacting a cyclic hydroxyalkyl carbonate with a polyisocyanate or a polyanhydride. 3. Method according to claim 1, characterized in that the compound with multiple cyclic carbonate groups is prepared by reacting a polyepoxide with CO2. 4. Method according to claim 1, characterized in that the compound with multiple cyclic carbonate groups is reacted with ammonia or with ammonium hydroxide. 5. Method according to claim 1, characterized in that said mixture further comprises a compound having multiple hydroxyl groups. 6. Method according to claim 1, characterized in that the polyacid comprises an anhydride. 7. Polyester which is the reaction product of a mixture comprising: (a) a polyol with multiple carbamate groups laterals, and (b) a polyacid characterized in that said polyol (a) is the reaction product of: (1) a compound that has multiple groups cyclic carbonate, and (2) ammonia, ammonium hydroxide or an amine primary. 8. Polyester according to claim 7, characterized in that the component (2) is ammonia or ammonium hydroxide. 9. Polyester according to claim 7, characterized in that the compound (1) is the reaction product of a cyclic hydroxyalkyl carbonate and a polyisocyanate or a polyanhydride. 10. Polyester according to claim 7, characterized in that the compound (1) is the reaction product of a polyepoxide and CO2. 11. Polyester according to claim 7, characterized in that said mixture further comprises a compound c) having multiple hydroxyl groups. 12. Hardenable coating composition that understands: (1) A polyester that is the reaction product of a mixture comprising:

(to)

a polyol having multiple lateral carbamate groups, characterized in that said polyol (a) is the reaction product of:

(i)

a compound that has multiple cyclic carbonate groups and

(ii)

ammonia, ammonium hydroxide or a primary amine, and

(b)

a polyacid, and

(2) A hardening agent that has multiple groups reactive with carbamate. 13. A hardenable coating composition according to claim 12, characterized in that the hardening agent is an aminoplast. 14. The curable coating composition according to claim 13, characterized in that the aminoplast is a melamine resin. 15. A hardenable coating composition according to claim 12, characterized in that the component (ii) is ammonia or ammonium hydroxide.